CN1600881A - Cu-Ni-Si alloy having good performance against fatigure - Google Patents
Cu-Ni-Si alloy having good performance against fatigure Download PDFInfo
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- CN1600881A CN1600881A CNA2004100684977A CN200410068497A CN1600881A CN 1600881 A CN1600881 A CN 1600881A CN A2004100684977 A CNA2004100684977 A CN A2004100684977A CN 200410068497 A CN200410068497 A CN 200410068497A CN 1600881 A CN1600881 A CN 1600881A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 title claims abstract description 27
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 239000012776 electronic material Substances 0.000 abstract description 5
- 230000035882 stress Effects 0.000 description 60
- 238000005096 rolling process Methods 0.000 description 23
- 230000032683 aging Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000005098 hot rolling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 238000005097 cold rolling Methods 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910018098 Ni-Si Inorganic materials 0.000 description 3
- 229910018529 Ni—Si Inorganic materials 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009661 fatigue test Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
Abstract
The purpose of this invention is to improve the fatigue properties of a high strength copper alloy utilized for the electronic material of a connector or the like. The Cu-Ni-Si based alloy comprises, by mass, 1.0 to 4.5% Ni and 0.2 to 1.2% Si, and the balance Cu with inevitable impurities. The alloy has a surface in which a compressive residual stress of 20 to 200 MPa is present, and is excellent in fatigue properties.
Description
[technical field]
The present invention relates to be used for the high strength copper alloy of electronic materials such as junctor.
[background technology]
In recent years, along with the development of the high-density installationization of electronic equipments such as Cell phone, digital camera, Kamera, electronic component tends to compactization significantly.Correspondingly, in the environment for use of element, the stress that repeats to put on metal parts has the trend of increase.In addition, along with the durability requirement to element uprises, the fatigue characteristic of metal parts there has been further requirement.Always, in the element that needs reliability especially, use be high strength type copper alloys such as the high beryllium copper of fatigue strength, titanium copper.
But the price of these high strength type copper alloys is compared with copper alloy always, because it is high to have high price, therefore, tries one's best all the time and uses cheap Cu-Ni-Si class alloy (for example, to refer to Patent Document 1 morely.)。
[patent documentation 1] spy opens the 2001-49369 communique
[summary of the invention]
Therefore, all the time, need further improve the fatigue characteristic of Cu-Ni-Si class alloy.
Usually, if improve the intensity of alloy, fatigue strength will improve.Cu-Ni-Si class alloy is a precipitation strength type copper alloy, no matter be to improve rolling working modulus, still increases the amount that helps the precipitate that intensity increases, and intensity is increased, but the improvement of the fatigue characteristic that cause for this high strength is limited.
The objective of the invention is improveing as the Cu-Ni-Si class alloy of the high strength copper alloy that is used for electronic material such as junctor.
Present inventors find: for the improvement of fatigue characteristic, following countermeasure is effective.
(1) Cu-Ni-Si class alloy, it is characterized in that: based on quality percentage (%) (following represent) with %, contain Ni:1.0～4.5%, Si:0.2～1.2%, nubbin is for to be made of Cu and unescapable impurity, and there is the compressive residual stress of 20～200Mpa in the surface.
(2) Cu-Ni-Si class alloy as claimed in claim 1 is characterized in that: the maximum concave surface degree of depth (following represent with Rv) on surface is below the 1 μ m.
(3) as above-mentioned (1)-(2) described Cu-Ni-Si class alloy, it is characterized in that: diameter is that the quantity of the above hotchpotch of 4 μ m is 100/mm
2Below.
(4) as above-mentioned (1)～(3) described Cu-Ni-Si class alloy, contain 0.05～0.3% Mg.
(5) as above-mentioned (1)～(4) described Cu-Ni-Si class alloy, contain 0.01～0.5% P.
(6) as each described Cu-Ni-Si class alloy of above-mentioned (1)～(5), contain 0.01～1.5% Sn.
(7) as each described Cu-Ni-Si class alloy of above-mentioned (1)～(6), contain 0.01～1.5% Zn.
(8) as each described Cu-Ni-Si class alloy of above-mentioned (1)～(7), adding total amount to it is more than one Fe, Co, Cr, Zr, Ti, Ag, Mn, Al below 1%.
The present invention has excellent fatigue characteristic, is applicable to the copper alloy of electronic materials such as terminal, junctor.
[best mode that carries out an invention]
Below, restriction basis of the present invention is described.
(1) Biao Mian unrelieved stress
When element running or loading and unloading,, apply the stress in bending in the elastic limit repeatedly to the metal parts of electronic components such as terminal, junctor, rly..Fatigue cracking in this case is from the outer surface of bend and produce, and this crackle becomes greatly gradually, up to broken loop member.If the surface at metallic substance applies compressive residual stress, can suppress the generation of crackle so, thereby increased fatigue lifetime.
If apply the residual surplus energy of compression more than the 20MPa on the surface, can improve fatigue characteristic.On the other hand, if compressive residual stress surpasses 200MPa, fatigue characteristic reduce on the contrary.So, the compressive residual stress value be defined as more than the 20MPa, below the 200MPa.
(2) surfaceness
The concave surface on surface plays the effect of recess, at first produces fatigue cracking at this concave surface place.Thereby, just can prolong fatigue lifetime if reduce the roughness on surface.
If when the maximum concave surface degree of depth Rv on surface surpassed 1 μ m, can reduce significantly fatigue lifetime.Thereby Rv is below 1 μ m for regulation.More preferably below 0.5 μ m.
(3) hotchpotch
Because this alloy type is a precipitation hardening type, has precipitate in matrix.In order to obtain necessary strength, precipitate in this alloy is trickle, but the hotchpotchs such as thick precipitate, crystallisate that surpass 4 μ m are unfavorable to intensity, the king-sized thick hotchpotch that surpasses 10 μ m can reduce bending machining performance, erosion, plating significantly, the reason that this is considered to promote crackle expansion causes reduce fatigue lifetime.
In the present invention, " hotchpotch " is meant general thicker crystallisate and the oxide compound that generates by the reaction in the liquation when dissolving, the sulfide etc. that generate in the process of setting of casting, further, " hotchpotch " is meant after the process of setting of casting, when process of cooling after the process of cooling after promptly solidifying, the hot rolling, after the solution treatment and ageing treatment, the precipitate that produces by evolution reaction in solid-phase matrix also comprises by the particle in the observed matrix of the SEM of this copper alloy.
" size of hotchpotch " passes through for example following step measurements with " number of hotchpotch ".After the cross section parallel with the rolling direction of raw material polished, etch was 2 minutes in the ferric chloride Solution of 47 ° of degree Beaume.Then, for prevent the charging and on sightingpiston the evaporation charcoal, and such material as the observation sample.For this sample, the use scanning electron microscope is 700 times secondary electron image at the many places of sample shooting ratio of enlargement." size of hotchpotch " is meant the smallest circle diameter that encases observed hotchpotch in the secondary electron image." number of hotchpotch " is meant in these secondary electron images that actual number gets observed every square millimeter hotchpotch number.In addition, by " number of hotchpotch " of every kind of classified calculating " size of hotchpotch ", just can know " number of hotchpotch " of every kind " size of hotchpotch " respectively.
If size surpass 4 μ m hotchpotch outnumber 100/mm
2, fatigue strength significantly reduces.So, the number of the hotchpotch that surpasses 4 μ m is defined as 100/mm
2Below.
(4) composition of copper alloy
1) Ni concentration: in Cu matrix, Ni and Si form intermetallics and separate out, and reduce and improve significantly intensity thereby suppress electric conductivity.Stipulate that this addition is that 1.0～4.5% reason is: be lower than at 1.0% o'clock, the amount of separating out is few and can not get enough intensity; If surpass 4.5%, when casting or hot-work, can generate the precipitate that is unfavorable for that intensity improves, not only can not get the intensity that matches with addition, and bring ill effect for hot workability and bending machining performance, and crystallisate and precipitate become thick, and outstanding, thereby the adaptation of precious metal plating is worsened from the helicitic texture end face.
2) Si concentration: Si can not bring baneful influence to electroconductibility, generates Ni with the Ni reaction
2The compound that Si forms.Therefore, the addition of only Si depends on the addition of Ni.The addition of Si is defined in 0.2～1.2% reason: be lower than at 0.2% o'clock, and identical with the situation of Ni, can not get enough intensity, if surpass 1.2%, produce the variety of issue identical with the situation of Ni.
3) Mg concentration: Mg can improve stress relaxation characteristics, but can make the composition of the heat-resisting separability deterioration of coating.The addition of Mg is defined in 0.05～0.3% reason: be lower than at 0.05% o'clock, stress relaxation characteristics can not get improving, if surpass 0.3%, the heat-resisting separability of coating reduces.
4) P concentration: P suppresses the growth of crystal grain by the constraint effect (the ピ Application stays the め effect) of the P-compound generation of Mg-P class, Ni-P class or Ni-Mg-P class, and then makes the crystal grain microminiaturization.This addition is being lower than at 0.01% o'clock and is not having effect, if surpass 0.5%, hot workability reduces and conductivity reduces significantly.
5) Sn concentration: when in electronic materials such as junctor, using copper alloy, implement coating at material surface sometimes.This coating mostly is Sn coating, as waste recovery and when recycling this material, material is contained under the situation of Sn, in order to remove Sn, needs to refine operation, but since production cost improve, so not preferred.In addition, wait in expectation and improve intensity by containing Sn, its addition is lower than at 0.01% o'clock, does not have effect, if surpass 1.5%, electric conductivity reduces so.
6) Zn concentration: carry out on copper alloy when zinc-plated, Zn makes the thermotolerances such as heat-resisting separability of tin coating improve, and its addition is lower than at 0.01% o'clock, does not have effect, if surpass 1.5%, electric conductivity reduces.
7) Fe, Co, Cr, Zr, Ti, Ag, Mn or Al:Fe, Co, Cr, Zr, Ti, Ag, Mn or Al have intensity and the stable on heating effect that improves Cu-Ni-Si class alloy.In addition, in these metals, Al and Mn also have the effect of improving hot rolling system performance.Reason is: because the avidity of these elements and sulphur is stronger, therefore form compound with sulphur, reduced the segregation of the sulphur of ingot particle surface, the segregation of sulphur is hot rolling system disruptive reason just.If the total content of Fe, Co, Cr, Zr, Ti, Ag, Mn or Al surpasses 1.0%, electric conductivity significantly reduces.Thereby, the total content of these metals is set in below 1.0%.
Then, the preparation method who obtains this alloy is described.
Usually, the preparation of ingot is undertaken by the direct chill casting method.For the direct chill casting method,, can generate the thick crystallisate and the precipitate of Ni-Si class at the process of setting in when casting.Carry out hot rolling system in heating under the temperature more than 800 ℃ after more than 1 hour, end temp is decided to be more than 650 ℃, by like this these thick hotchpotchs being solid-solubilized in the matrix.But, if more than 900 ℃, will existing, Heating temperature produces the disruptive problem when producing a large amount of iron scales, hot rolling system, therefore, Heating temperature is preferably at 800 ℃～900 ℃.
In order to utilize ageing treatment to obtain high-intensity material, can also carry out solution heat treatment before the ageing treatment, solution heat treatment temperature height, Ni, the Si solid solution capacity in matrix increases, from matrix, separate out the intermetallics of Ni-Si class during ageing treatment minutely, further improved intensity.In order to obtain this effect, the temperature of wishing solution heat treatment is more than 750 ℃, preferred 800 ℃～950 ℃.And, for copper alloy of the present invention, if temperature is 950 ℃, Ni, Si fully are solid-solubilized in the matrix, when surpassing 950 ℃ of temperature, during solution heat treatment, the oxidation of material surface is very violent, and in order to remove zone of oxidation, the burden of pickling process is very big, therefore, recommend the treatment temp of use below 950 ℃.
In addition, in order to improve the intensity after the ageing treatment further, can carry out cold rolling before ageing treatment, the intensity of the high more acquisition of this working modulus is just big more.This working modulus is the required intensity of copper alloy of the present invention, can select suitably according to processing characteristics.
The ageing treatment of carrying out in order to obtain desired intensity and electroconductibility, need make aging temperature is 300～650 ℃.When being lower than 300 ℃, ageing treatment is very time-consuming, and if be higher than 650 ℃, the Ni-Si particle becomes thick and economical inadequately, if surpass 700 ℃ again, and the complete solid solution of Ni and Si, intensity and electroconductibility do not improve.When under 300～650 ℃ of scopes, carrying out ageing treatment,, just can obtain enough intensity and electroconductibility if the time of ageing treatment is 1～10 hour.
And, for copper alloy of the present invention,, can after ageing treatment, carry out cold rolling in order further to improve its intensity, heat-treat (stress relieving) then.
For example, can carry out the adjustment of surfaceness by rolling, grinding etc.In actually operating, the rolling roller of use adjustment sheet surface roughness etc. is rolled, thereby can adjust the surfaceness of this copper alloy.In addition, in the operation after rolling,, for example, can grind by implementing the different polishing of hole thickness (the thick さ of め) for material surface, thus the surfaceness of adjustment material.
The diameter of rolling roller that can be by adjusting last cold rolling and the working modulus that once connects reach the adjustment to the unrelieved stress of material surface.Promptly be that if reduce the diameter of roller, the unrelieved stress on surface changes stress under compression into by tensile stress.If the working modulus that reduces once to connect, the unrelieved stress on surface changes stress under compression into by tensile stress.
[embodiment]
(1) embodiment 1
In the high frequency smelting furnace, the copper alloy that the various one-tenth of melting are grouped into is cast into the ingot that thickness is 20mm.Then, fully be solid-solubilized in the matrix in order to make Ni and Si, Heating temperature be more than 800 ℃ and the temperature of 900 ℃ of less thaies under, heat this ingot more than 2 hours, carry out hot rolling system then, and makes that end temp is more than 650 ℃, thickness reaches 8mm.Then, after carrying out surfacing, make the substrate that thickness is 3mm for the iron scale of removing the surface by cold rolling.Then, under 400 ℃～600 ℃ temperature, annealed 5 hours.Here, after carrying out surfacing, forming thickness by cold rolling is the substrate of 0.5mm for the iron scale of removing the surface once more.Then, under 850 ℃～950 ℃ temperature, carry out 10 minutes solution heat treatment after, cold rolling is to 0.2mm.Simultaneously, in each component of 400 ℃～600 ℃, obtain to divide the ageing treatment of carrying out in addition 5 hours under the temperature of top temperature.
In addition, in order to adjust the unrelieved stress of material surface, the diameter of the rolling roller of final cold rolling and the working modulus that once connects are adjusted.
Promptly be,
1) rolling roller: the preparation diameter is the rolling roller of 50mm, 100mm, 200mm.If reduce the diameter of roller, the unrelieved stress on surface becomes stress under compression by tensile stress.
2) working modulus: if the working modulus that reduces once to connect promptly is that in the operation of rolling of 0.5mm～0.2mm, if increase the number of times that connects to roller mill, so Biao Mian unrelieved stress becomes stress under compression by tensile stress.
Sample for after the processing carries out the mensuration and the fatigue test of tension test, electric conductivity, stress relaxation, the surperficial maximum concave surface degree of depth and unrelieved stress.
(a) mensuration of tension test and electric conductivity
According to JISZ 2241, use JIS13B tension test sheet, carry out tension test along being parallel to rolling direction, obtain 0.2% yielding stress.Four-terminal method according to JISH0505 is measured electric conductivity (%IACS), estimates electroconductibility thus.
(b) stress relaxation rate is measured
In 150 ℃ atmosphere, make 80% stress in bending (σ) of sample load 0.2% proof stress, and the offset deviation of only trying to achieve according to through type (1) and make the sample bending, kept such state 1000 hours, stress relaxation rate after estimating 1000 hours with %, this relaxation rate is stress relaxation characteristics.
Y=(2 * σ * L
2) (3 * E * t) ... formula (1)
(E: Young's modulus=120GPa), t: thickness of slab, L: spring length, y: offset deviation)
(c) the maximum concave surface degree of depth Rv in surface
According to the concave surface bottom line of the roughness curve that JISB0601 measured as the maximum concave surface degree of depth.
(d) unrelieved stress
Collecting wide is that 20mm, length are the rectangle sample of 200mm, makes the length direction of sample consistent with rolling direction.Carry out etch with ferric chloride in aqueous solution from side, try to achieve the radius-of-curvature of sample curved surface, and calculate unrelieved stress.Measure by changing double-edged etch amount.Obtain as shown in Figure 1 thickness direction residual be coated with distribution curve of stress (must rattan one: residual stress and bending, interior Tian Laohe garden society, (1988), p.46 of being coated with).Obtain the residual-stress value of pro and con from this curve, the mean value of two values is defined as the residual-stress value on surface.
(e) fatigue test
According to JISZ 2273, carry out the fatigue test of planar inverted bending (two shake リ plane bent げ).Collecting wide is the rectangle sample of 10mm, and makes the length direction of sample consistent with rolling direction.According to the relation between the distance (L) of additional maximum stress (σ), amplitude (f) and the fulcrum and the stress point of specimen surface, set test conditions.
L=√ (3t Ef/ (2 σ)) (t: sample thickness, E: Young's modulus (=120GPa))
Number of times (Nf) when measuring sample fracture.Measure 4 times, try to achieve the Nf that measures for 4 times and on average plant.
[table 1]
| Sample No. | Component (quality %) | 0.2% proof stress (MPa) | Unrelieved stress (MPa) | Additional stress, σ (MPa) | Fatigue lifetime (thousand times) | |||
| ??Ni | ??Si | ??Mg | ||||||
| Example | ????1 | ? ? ? ??2.49 | ? ? ? ??0.45 | ? ? ? ??0.12 | ????703 ? ????704 ? ????701 ????690 | ????-169 ? ????-81 ? ????-43 ????-23 | ? ? ? ????500 | ????3058 ? ????2540 ? ????1557 ????1063 |
| ????2 | ||||||||
| ????3 | ||||||||
| ????4 | ||||||||
| Comparative example | ????5 | ? ? ? ? ??2.49 | ? ? ? ? ??0.45 | ? ? ? ? ??0.12 | ????698 ? ????705 ? ????703 ? ????695 ? ????710 | ????3 ? ????13 ? ????95 ? ????165 ? ????-220 | ? ? ? ? ????500 | ????869 ? ????672 ? ????304 ? ????193 ? ????977 |
| ????6 | ||||||||
| ????7 | ||||||||
| ????8 | ||||||||
| ????9 | ||||||||
| Example | ????10 | ? ??3.48 | ? ??0.64 | ? ??0.13 ? | ????780 ????755 | ????-155 ????-66 | ? ????550 | ????2986 ????2234 |
| ????11 | ||||||||
| Comparative example | ????12 | ??3.48 | ??0.64 | ??0.13 | ????760 | ????15 | ????550 | ????654 |
| Example | ????13 | ??2.21 | ??0.42 | ??0.11 | ????685 ????690 | ????-184 ????-78 | ????500 | ????3050 ????2497 |
| ????14 | ||||||||
| Comparative example | ????15 | ??2.21 | ??0.42 | ??0.11 | ????683 | ????7 | ????500 | ????604 |
In table 1, expression has changed the fatigue lifetime of the various Cu-Ni-Si class alloys of surface residual stress.For the various samples of table 1, the hotchpotch number that Rv=0.3～0.4 μ m, size is surpassed 4 μ m is adjusted to 100/mm
2Below.
If apply the unrelieved stress of compression (bearing) on the surface, can prolong fatigue lifetime so.But,, reduce fatigue lifetime so (No.9) if compressive residual stress surpasses 200MPa.
And the surfaceness of roller, the kind of lubricating oil, the tension force when rolling, the multiple factors such as mechanical characteristics of rolling stock can be brought influence to residual-stress value.Thereby, though specifically can not be only by changing as the rolling roller diameter of parameter and connect number of times, and merely determine unrelieved stress, list the condition shown in No.2 and the No.6 below, only for referencial use.
No.2: roller diameter 50mm, connect number of times 12 times
No.6: roller diameter 200mm, connect number of times 6 times
(2) embodiment 2
Under the same preparation condition of embodiment 1, the preparation copper alloy is wherein adjusted the various compositions in the composition that is shown in table 2.In addition, to each specimen surface compress (bearing) unrelieved stress (100～-150MPa), the hotchpotch number that Rv=0.3～0.4 μ m, size is surpassed 4 μ m is adjusted into 100/mm
2Below.
[table 2]
| Sample No. | Component (quality %) | 0.2% yielding stress (MPa) | Electric conductivity (% IACS) | Stress relaxation rate (%) | Additional stress, σ (MPa) | Fatigue lifetime (thousand times) | ||||||
| ??Ni | ??Si | ??Mg | ????P | ????Sn | ????Zn | |||||||
| Example of the present invention | ????16 | ??2.48 | ??0.46 | ??0.17 | ????＜0.01 | ????＜0.01 | ????＜0.01 | ????703 | ????43 | ????10 | ????500 | ????2676 |
| ????17 | ??2.54 | ??0.39 | ??0.12 | ????0.12 | ????＜0.01 | ????＜0.01 | ????701 | ????45 | ????11 | ????500 | ????2873 | |
| ????18 | ??2.52 | ??0.44 | ??0.09 | ????＜0.01 | ????1.1 | ????＜0.01 | ????698 | ????41 | ????12 | ????500 | ????2608 | |
| ????19 | ??2.54 | ??0.45 | ??0.06 | ????＜0.01 | ????＜0.01 | ????1.0 | ????703 | ????40 | ????11 | ????500 | ????2771 | |
| ????20 | ??2.48 | ??0.44 | ??0.00 | ????＜0.01 | ????＜0.01 | ????＜0.01 | ????704 | ????44 | ????28 | ????500 | ????2732 | |
| Comparative example | ????21 | ??2.53 | ??0.47 | ??0.07 | ????0.6 | ????＜0.01 | ????＜0.01 | Produce during hot rolling system and break | ||||
| ????22 | ??2.50 | ??0.44 | ??0.19 | ????＜0.01 | ????2.0 | ????＜0.01 | ????705 | ????31 | ????11 | ????500 | ????2953 | |
| ????23 | ??2.53 | ??0.47 | ??0.16 | ????＜0.01 | ????＜0.01 | ????2.2 | ????695 | ????32 | ????13 | ????500 | ????2695 | |
| ????24 | ??0.97 | ??021 | ??0.13 | ????＜0.01 | ????＜0.01 | ????＜0.01 | ????578 | ????33 | ????17 | ????450 | ????796 | |
| ????25 | ??4.54 | ??0.94 | ??0.11 | ????＜0.01 | ????＜0.01 | ????＜0.01 | Produce during hot rolling system and break | |||||
Find that the present invention's example 16-20 has excellent electric conductivity and fatigue characteristic.Because example 20 of the present invention does not contain Mg, therefore to compare with the present invention's example 16-19, stress relaxation characteristics is poor.
With respect to these,, in addition,, therefore when hot rolling system, produce and break, thereby abandoned follow-up processing because comparative example 25Ni is more because the P concentration of comparative example 21 is higher.Comparative example 22 and 23 Sn or Zn concentration height separately, electric conductivity reduces.Comparative example 24 is with to give surface compression (bear) residual-stress value irrelevant, and the content of Ni and Si is few, and intensity is low, thereby lack fatigue lifetime.
(3) embodiment 3
For the Cu-Ni-Si alloy that component is adjusted into Cu-2.53%Ni-0.48%Si-0.16%Mg, change the final roughness of roller when rolling, prepare surperficial maximum concave surface degree of depth Rv difference, thickness is the sample of 0.15mm.Preparation condition beyond the roughness is identical with embodiment 1.And, the unrelieved stress of each sample is adjusted to-100～-scope of 150MPa (compressive residual stress).The hotchpotch number that size is surpassed 4 μ m is adjusted to 100/mm
2Below.
Adjust the surface tissue of sample by the surfaceness of adjusting final rolling roller.Promptly be, reserve centre line average roughness Ra is the rolling roller of the identical roller diameter (100mm) of 0.5,1.0,1.5 μ m, changes the rolling pressure when rolling.Use the little roller of Ra and reduce rolling load, surperficial maximum concave surface degree of depth Rv just reduces thereupon, uses the big roller and the rolling load that raises of Ra, and surperficial maximum concave surface degree of depth Rv just increases thereupon.
[table 3]
| Sample No. | 0.2% yielding stress (MPa) | Surface full depth μ m | Fatigue lifetime (thousand times) | |
| Example | ????26 | ????703 | ????0.27 | ????3058 |
| ????27 | ????704 | ????0.44 | ????2700 | |
| ????28 | ????701 | ????0.7 | ????2360 | |
| ????29 | ????690 | ????0.93 | ????2150 | |
| Comparative example | ????30 | ????698 | ????1.15 | ????1780 |
| ????31 | ????705 | ????1.53 | ????1557 |
Fatigue lifetime when table 3 expression additional stress σ is 500MPa.If Rv is big, just reduce fatigue lifetime, and do not reach 2,000,000 times.
(4) embodiment 4
Being adjusted into the Cu-Ni-Si alloy of Cu-2.53%Ni-0.48%Si-0.16%Mg, under the condition identical, be processed into 0.2mm for component with embodiment 1.And, adjust the Heating temperature before the hot rolling system, the temperature of solution heat treatment, make the hotchpotch number difference that 4 μ m are above.
The Rv of each sample is adjusted to the scope of 0.4～0.5 μ m, unrelieved stress is adjusted to-70～-scope of 80MPa (compressive residual stress).
[table 4]
| Sample No. | 0.2% yielding stress (MPa) | Hotchpotch several/mm 2 | Heating temperature before the hot rolling system (℃) | The solutionizing temperature (℃) | Fatigue lifetime (thousand times) | |
| Example of the present invention | ????32 | ????703 | ????25 | ????900 | ????950 | ????3058 |
| ????33 | ????704 | ????47 | ????850 | ????900 | ????2540 | |
| ????34 | ????701 | ????86 | ????850 | ????850 | ????2120 | |
| Comparative example | ????35 | ????690 | ????125 | ????850 | ????800 | ????1557 |
| ????36 | ????698 | ????150 | ????800 | ????800 | ????869 |
Fatigue stress when table 4 expression additional stress σ is 500MPa.Therefrom as can be seen, if the hotchpotch number surpasses 100/mm
2, just reduce fatigue lifetime.
[simple declaration of accompanying drawing]
The residual stress distribution synoptic diagram of [Fig. 1] thickness of slab direction.
Claims (8)
1.Cu-Ni-Si class alloy, it is characterized in that: based on quality percentage (%) (following represent) with %, contain Ni:1.0～4.5%, Si:0.2～1.2%, the copper alloy of nubbin for constituting by Cu and unavoidable impurities, there is the unrelieved stress of 20～200MPa in the surface.
2. the described Cu-Ni-Si class of claim 1 alloy is characterized in that: the maximum concave surface degree of depth on surface (following represent with Rv) is below the 1 μ m.
3. the described Cu-Ni-Si class of claim 1-2 alloy is characterized in that: diameter is that the above hotchpotch of 4 μ m is 100/mm
2Below.
4. the described Cu-Ni-Si class of claim 1～3 alloy is characterized in that: contain Mg:0.05～0.3%.
5. the described Cu-Ni-Si class of claim 1～4 alloy is characterized in that: contain P:0.01～0.5%.
6. each described Cu-Ni-Si class alloy of claim 1～5 is characterized in that: contain Sn:0.01～1.5%.
7. each described Cu-Ni-Si class alloy of claim 1～6 is characterized in that: contain Zn:0.01～1.5%.
8. each described Cu-Ni-Si class alloy of claim 1～7 is characterized in that: in total amount is 1% scope, add more than one the metal among Fe, Co, Cr, Zr, Ti, Ag, Mn, the Al.
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| JP283522/2003 | 2003-07-31 | ||
| JP2003283522A JP4255330B2 (en) | 2003-07-31 | 2003-07-31 | Cu-Ni-Si alloy member with excellent fatigue characteristics |
| JP283522/03 | 2003-07-31 |
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| CN100408708C CN100408708C (en) | 2008-08-06 |
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| JP (1) | JP4255330B2 (en) |
| KR (1) | KR100642571B1 (en) |
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Also Published As
| Publication number | Publication date |
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| KR100642571B1 (en) | 2006-11-10 |
| KR20050014758A (en) | 2005-02-07 |
| TW200510552A (en) | 2005-03-16 |
| TWI287584B (en) | 2007-10-01 |
| JP2005048262A (en) | 2005-02-24 |
| CN100408708C (en) | 2008-08-06 |
| JP4255330B2 (en) | 2009-04-15 |
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Effective date of registration: 20060714 Address after: Tokyo, Japan, Japan Applicant after: Nippon Mining & Metals Co., Ltd. Address before: Kanagawa Applicant before: Nippon Mining Co. |
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Owner name: JX NIPPON MINING + METALS CORPORATION Free format text: FORMER NAME: NIPPON MINING + METALS CO., LTD. |
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| CP03 | Change of name, title or address |
Address after: Tokyo, Japan, Japan Patentee after: JX Nippon Mining & Metals Corporation Address before: Tokyo, Japan Patentee before: Nippon Mining & Metals Co., Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan, Japan Patentee after: JX NIPPON MINING & METALS CORPORATION Address before: Tokyo, Japan, Japan Patentee before: JX Nippon Mining & Metals Corporation |
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Address after: No. 10-4, erdingmu, tiger gate, Tokyo port, Japan Patentee after: JKS Metal Co.,Ltd. Address before: Tokyo, Japan Patentee before: JKS Metal Co.,Ltd. |